Nitrogen-doped carbon nanotubes are selective and robust electrocatalysts for CO2 reduction to formate in aqueous media without the use of a metal catalyst. Polyethylenimine (PEI) functions as a co-catalyst by significantly reducing catalytic overpotential and increasing current density and efficiency. The co-catalysis appears to help in stabilizing the singly reduced intermediate CO2(•-) and concentrating CO2 in the PEI overlayer.

temperature sensors, [10] light emitting diodes, [11] radio frequency devices, [12] field effect transistors, [13] epidermal electronics, [2] and integrated circuits. [4] To integrate these stretchable electronics into a power-independent stretchable system in an elegant way, stretchable energy conversion/storage devices become of paramount importance. [14][15][16][17] Although over the decades, stretchable energy conversion devices like organic solar cells, [6] triboelectric nanogenerators, [18] and various piezoelectric devices [19] have been of great interest, energy storage devices such as electrochemical supercapacitors (SCs) have also been intensively explored for various applications. Their unique features of fast chargedischarge rate, high power density, long operation life, and modest energy excellently complement batteries. [17,20] However, most of the existing stretchable supercapacitors can only be stretched in one direction, whereas retaining functionality during multidirectional stretching is essential for many applications. Moreover, many of the stretchable SCs are affected by the applied strains, and are easily damaged if unexpected stretching happens to be larger than the predefined stretchability of the device in fabrication. [21] Among the available materials, carbon-based nanomaterials have been extensively utilized for stretchable SC electrodes due to their high specific surface area, structural integrity, and low cost. [14,17,22] For example, Yu et al. presented stretchable Stretchable supercapacitors have received increasing attention due to their broad applications in developing self-powered stretchable electronics for wearable electronics, epidermal and implantable electronics, and biomedical devices that are capable of sustaining large deformations and conforming to complicated surfaces. In this work, a new type of highly stretchable and reliable supercapacitor is developed based on crumpled vertically aligned carbon nanotube (CNT) forests transferred onto an elastomer substrate with the assistance of a thermal annealing process in atmosphere environment. The crumpled CNT-forest electrodes demonstrated good electrochemical performance and stability under either uniaxial (300%) or biaxial strains (300% × 300%) for thousands of stretching-relaxing cycles. The resulting supercapacitors can sustain a stretchability of 800% and possess a specific capacitance of 5 mF cm −2 at the scan rate of 50 mV s −1 . Furthermore, the crumpled CNT-forest electrodes can be easily decorated with impregnated metal oxide nanoparticles to improve the specific capacitance and energy density of the supercapacitors. The approach developed in this work offers an alternative strategy for developing novel stretchable energy devices with vertically aligned nanotubes or nanowires for advanced applications in stretchable, flexible, and wearable electronic systems.

Insights into the growth of high edge density carbon nanostructures were achieved by a systematic parametric study of plasma-enhanced chemical vapor deposition (PECVD). Such structures are important for electrode performance in a variety of applications such as supercapacitors, neural stimulation, and electrocatalysis. A morphological trend was observed as a function of temperature whereby graphenated carbon nanotubes (g-CNTs) emerged as an intermediate structure between carbon nanotubes (CNTs) at lower temperatures and vertically oriented carbon nanosheets (CNS), composed of few-layered graphene, at higher temperatures. This is the first time that three distinct morphologies and dimensionalities of carbon nanostructures (i.e., 1D CNTs, 2D CNSs, and 3D g-CNTs) have been synthesized in the same reaction chamber by varying only a single parameter (temperature). A design of experiments (DOE) approach was utilized to understand the range of growth permitted in a microwave PECVD reactor, with a focus on identifying graphenated carbon nanotube growth within the process space. Factors studied in the experimental design included temperature, gas ratio, catalyst thickness, pretreatment time, and deposition time. This procedure facilitates predicting and modeling high edge density carbon nanostructure characteristics under a complete range of growth conditions that yields various morphologies of nanoscale carbon. Aside from the morphological trends influenced by temperature, a relationship between deposition temperature and specific capacitance emerged from the DOE study. Transmission electron microscopy was also used to understand the morphology and microstructure of the various high edge density structures. From these results, a new graphene foliate formation mechanism is proposed for synthesis of g-CNTs in a single deposition process.

We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k0, approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film.

The growth of carbon nanotubes (CNTs) on polycrystalline silicon substrates was studied to improve the design of CNT field emission sources for microelectromechanical systems (MEMS) applications and vacuum microelectronic devices (VMDs). Microwave plasmaenhanced chemical vapor deposition (PECVD) was used for CNT growth, resulting in CNTs that incorporate the catalyst particle at their base. The kinetics of CNT growth on polysilicon were compared to growth on Si (100) using the model of Deal and Grove, finding activation energies of 1.61 and 1.54 eV for the nucleation phase of growth and 1.90 and 3.69 eV for the diffusion-limited phase on Si (100) and polysilicon, respectively. Diffusivity values for growth on polysilicon were notably lower than the corresponding values on Si (100) and the growth process became diffusion-limited earlier. Evidence favors a surface diffusion growth mechanism involving diffusion of carbon precursor species along the length of the CNT forest to the catalyst at the base. Explanations for the differences in activation energies and diffusivities were elucidated by SEM analysis of the catalyst nanoparticle arrays and through wide-angle X-ray scattering (WAXS) of CNT forests. Finally, methods are presented to improve adhesion of CNT films during operation as field emitters, resulting in a 2.5x improvement.